Double metal cyanides complexed with an alcohol aldehyde or ketone to increase catalytic activity



United States Patent 3,427,334 DOUBLE METAL CYANIDES COMPLEXED WITH ANALCOHOL ALDEHYDE OR KETONE TO IN- CREASE CATALYTIC ACTIVITY Robert J.Belner, Akron, Ohio, assignor to The General Tire & Rubber Company,Akron, Ohio, a corporation of Ohio No Drawing. Original application Feb.14, 1963, Ser. No. 258,595, now Patent No. 3,278,458, dated Oct. 11,1966. Divided and this application Jan. 13, 1966, Ser. No. 520,378 US.Cl. 260429 18 Claims Int. Cl. C08g 23/00; B01j 11/00 ABSTRACT OF THEDISCLOSURE A double metal cyanide complex compound is provided, whereinone of the metals of said complex compound is selected from the groupconsisting of Zn (II), Fe (II), Fe (III), Co (11), Ni (II), Mo IV), Mo(VI), Al (III), V (IV), V (V), Sr (H), W (W), W (VI), Mn (II), and Cr(III), and mixtures thereof, and wherein the other metal of said complexcompound is selected from the group consisting of Fe (:11), Fe (III), Co(II), Co (III), Cr (II), Cr (III), Mn (II), Mn III), V (IV), and V (V),and mixtures thereof, containing, in an amount sufficient to increasethe activity of said complex for the polymerization of organic cyclicoxides, at least one organic material selected from the group consistingof an alcohol, an aldehyde, and a ketone, said organic material beinginert to polymerization by said compound and further being complexedwith said compound, said compound containing at least a majority of CN*bridging groups. These compounds are useful in polymerizing epoxidessuch as propylene oxide, ethylene oxide, allyl glycidyl ether and thelike to make polyethers.

This is a division of application Ser. No. 258,595 filed Feb. 14, 1963,now United States Patent No. 3,278,458 granted Oct. 11, 1966.

The present invention relates to double metal cyanid complexes useful ascatalysts and to methods for making said catalysts.

'It is an object of the present invention to provide double metalcyanide complexes useful as catalysts.

It is another object of this invention to provide a method for makingdouble metal cyanide complexes useful as catalysts.

These and other objects and advantages of the present invention willbecome more apparent to those skilled in the art from the followingdetailed description and examples.

According to the present invention it has been discovered that certaindouble metal cyanide complexes are useful as catalysts (or as initiatorsas they can be consumed during polymerization) for the polymerization oforganic compounds having at least one ring of from 2 to 3 carbon atomsand one oxygen atom like ethylene oxide, propylene oxide, allyl glycidylether, oxetane, and so forth.

Many of the polymers obtained by the method of this invention areentirely or almost entirely amorphous in contrast to the polymers ofsimilar organic oxides obtained using other catalysts. On the otherhand, some of the polymers obtained such as those from isobutylene oxideare entirely crystalline or resinous so that they can be used to makehard and tough articles of manufacture. The rubbery polymers preparedusing the catalysts of this invention are free of gel. In certain caseswhere diepoxides or dioxetanes are also copolymerized with the epoxideor oxetane monomers some gel may be observed. Although these rubbery orelastomeric polymers when unstretched are amorphous as shown by X-ray,they do show some indication of orientation on stretching. Many of thesepolymers are linear and have very little branching depending on the typeof monomers used. Polymers having very high viscosities are obtained bythe present invention which still are millable, forming smooth sheets onthe rubber mill, processable, extrudable and so forth. Gum stocksexhibit high elongation and are snappy. In contrast to many polymers,the polymers of the present invention exhibit high solution viscositiesyet low Mooney viscosities. These rubbers, also, exhibit the good lowtemperature stiffening properties of the nitrile rubbers.

A tubeless tire comprises a tread portion and sidewalls which may beextruded from one piece of stock. The tread or the entire rubberymaterial of the tire can be one of the amorphous polymers or copolymersof this invention. Of course, when white sidewall tires are being made,the tread and sidewalls can be extruded separately. There can be one ormore plies depending on the service for which the tire is designed. Thefabric plies comprise rayon or nylon fabric or other textile fabriccalendered or coated with rubbery material. The ends of the fabric pliesare generally wrapped around beads which can comprise steel wires, andthe inner surface of the tire contains a layer of a butyl rubber (acopolymer of about 99.5% isobutylene and the balance a diolefin of from4 to 8 carbon atoms) compound or composition or other suitable material(such as a copolymer of the present invention of the desired thickness)for preventing diffusion of air or gas from the interior of the tire.The butyl may be precured or partially precured. Where the tie is to beused with a tube, the butyl liner can be omitted. The tire can be builtby conventional procedures On the usual tire building machinery andcured under pressure in suitable molds at from about 280 to 310 F. forfrom about 15 to 60 minutes or more. The various plies, tread stock andso forth can be tackified with heptane or similar solvents, or withadhesives of a polymer of this invention as a 15% solids in a solventsuch as heptane, at the time they are laid up on the building drum.Cushion stock and inserts can be added during tire building between thebreaker, if used, and the various plies as necessary to improve ridingand wearing qualities as well as to obtain the desired contour and crosssection in the finished tire. Chafer strips, also, can be added duringthe building operation in the vicinity of the beads to minimize chafingcaused by contact with the rim. All of the rubbery material employed inmaking the tire can be of one or more of the polymers or copolymers ofthe present invention. Moreover, the tread, sidewalls, and ply stockscan be of the same or a different polymer (in which the monomers orproportions thereof are varied) of the present invention depending uponthe properties required in the particular structure involved. Variouscuring systems can be used with these compositions to get the desireddegree of curing in the final tire.

Where the carcass or one or more of the ply stocks, side-Walls and thelike are made of a rubbery material, other than that of the presentinvention such as a rubbery copolymer of butadiene-1,3 and styrene,natural rubber, cis-polyisoprene, cis-polybutadiene-1,3 and so forth asWell as blends thereof including those with reclaim rubber, adhesives orcements containing those rubbers with varying amounts of the rubberypolymers or copolymers of this invention can be used if necessary toobtain the desired adhesion between the other rubbery compositions andthe rubbery copolymers of the present invention. For example, where itis desired to join an extruded tread and sidewall stock of a compositionof rubbery polymer of this invention, for example a rubbery polymer ofpropylene oxide (P0) or a rubbery copolymer of propylene oxide and allylglycidyl ether (AGE), to a carcass of a rubbery butadiene1,3/styrene(BDN-STY) copolymer stock, a layer of a cement of a major amount of theBDN-STY copolymer and a minor amount of the PO-AGE copolymer is brushedon the outer surface of the carcass and dried. Next, a cement layer ofabout equal portions of the BDN-STY copolymer and the PO-AGE copolymeris applied to the first layer and dried followed by a third layer of aminor amount of BDN-STY copolymer and a major amount of the PO- AGEcopolymer and dried. This last layer is designed to be in contact withthe tread and sidewall when assembled. The carcass having the threelayers of cement is then ready for application of the side walls andtread. After final assembly and curing, the tread and sidewalls adhereto the carcass. Where the tread, sidewalls, ply stocks and others aremade of blends of the polymers of the present invention and naturalrubber, rubbery butadiene-l,3/styrene copolymers etc., one or moresimilar cement layers can be used if desired.

The catalyst is most usefully prepared by reacting a transition metalcyanide complex with a metal salt in aqueous media. Removal of asubstantial amount or all of the water present in the catalyst is verydesirable to enhance the activity of the catalyst although it wouldappear that removal of all the water is not practicable and may not bedesirable. One way to remove most of the water and to enhance evenfurther the activity of the catalyst is to treat it with an additionalcomplexing or coordinating material such as an alcohol, ether, ester,sulfide, ketone, aldehyde, amide and/ or nitrile.

In general the catalysts employed in the present invention have thefollowing rational formulae:

M is a metal ion that forms a metal-oxygen bond that is relatively morestable than the coordinate bond between the metal and the nitrogen atomof the cyano, CN, group. On the other hand, M is a transition metal ionthat has more than one stable valence form and forms a relatively strongcovalent bond with the carbon atom of the CN group. An individualcatalyst can contain more than one type of M or M metal ion in itsstructure. The grouping of these metals, with the cyanide ion sharingelectrons with the two metal ions, usually exists in polymeric form asfollows: (MCN M NC-M) where n is a number, and super 3-dimensionalpolymers can be formed depending on the coordination numbers of M and M.Moreover, of those metal ions that produce active cyanide catalysts, allcan coordinate with six groups. Most of the hexacyanoferrates (III),including zinc hexacyanoferrate (III), have a cubic face-centeredlattice as the basic structure.

The CN group in the catalyst is the bridging group, and can constituteall of the bridging groups in the catalyst. However, other bridginggroups can be present in the catalyst so long as the catalyst contains.at least a majority of CN- bridging groups. Thus, r and t are numbersand r is greater than t. t is zero when only the CN group is thebridging group. Other bridging groups, X in the right hand formulaabove, which can be present with the CN- group, can be F-, Cl, Br, I,OH-, NO, CO, H O, NO C O or other acid radical, 80 CNO" (cyanate), CNS(thiocyanate), NCO- (isocyanate), and NCS- (isothiocyanate) and soforth.

In the above formulae M is preferably a metal selected from the groupconsisting of Zn (II), Fe (II), Fe (III), Co (II), Ni (H), Mo (IV), Mo(VI), Al (III), V (IV), V (V), Sr (II), W (IV), W (VI), Mn (II) and Cr(HI). On the other hand, M is preferably a metal selected from the groupconsisting of Fe (II), Fe (III), Co (H), Co (IH), Cr (II), Cr (III), Mn(H), Mn (III), V (IV) and A150, b and C are nu b rs whose values arefunctions of the valences and coordination numbers of M and M, and thetotal net positive charge on M times a should be equal essentiallly tothe total net negative charge on [M(CN) or [M'[(CN),(X) times c. In mostinstances b corresponds to the coordination number of M and is usually6.

Examples of catalysts which fall within the above description and whichmay be used are zinc hexacyanoferrate (III), zinc hexacyanoferrate (II),nickel (II) hexacyanoferrate (II), nickel (H) hexacyanoferrate (III),zinc hexacyanoferrate (HI) hydrate, cobalt (H) hexacyanoferrate (II),nickel (H) hexacyanoferrate (HI) hydrate, ferrous hexacyanoferrate(III), cobalt (II) hexacyano cobaltate (III), zinc hexacyano cobaltate(II), zinc hexacyanomanganate (II), zinc hexacyano chromate (III), zinciodo pentacyanoferrate (III), cobalt (II) chloropentacyanoferrate (II),cobalt (II) bromopentacy-anoferrate (II), iron (II)fluoropentacyanoferrate (III), zinc chlorobromotetracyanoferrate (IH),iron (III) hexacyanoferrate (IH), aluminum dichlorotetracyanoferrate(III), molybdenum (IV) bromopentacyanoferrate (IH), molybdenum (VI)chloropentacyanoferrate (II), vanadium (IV) hexacyanochromate (II),vanadium (V) hexacyanoferrate (III), strontium (II) hexacyano manganate(III), tungsten (IV) hexacyano vanadate (IV), aluminum chloropentacyanovanadate (V), tungsten (VI) hexacyanoferrate (IH), manganese (H)hexacyanoferrate (H), chromium (III) hexacyanoferrate (III), and soforth. Still other cyanide complexes can be used such as Zn[Fe(CN) NO],Zn [Fe(CN) NO Zn[Fe(CN) CO], Zn[Fe(CN) H O], Fe[Fe(CN) OH],

and the like. Mixtures of these compounds can be employed.

In general, the complex catalysts of this invention are prepared byreacting aqueous solutions of salts which give a precipitate of a metalsalt of a transition metal complex anion. For example where M is a metalion which precipitates complex anion salts e.g., Zn++. a, b and c inthis equation are numbers but are not necessarily equal on both sides ofthe equatron since their values, again, are functions of the valencesand coordination numbers of M, M and M and possibly Y.and Z. Z is ahalide or other anion e.g. Cl; M" is a hydrogen ion or a metal ion whosecomplex anion salts are soluble in water or other solvent e.g., K+ orCa++; M is a complexing transition metal ion, e.g. Fe+++; and Y icsI acomplexing anion, e.g. CN. Excess MaZ may be use Little if any of theother bridging groups or ligands which can be used to replace part ofthe cyano groups (CN-) are usually introduced into the complex by use ofthe salt MaZ. Rather, they are introduced into the complex by employingthe M[M'(Y),,] salt containing the ligand or more correctly a salthaving the formula M"[M((CN),(X) in which t is a number dependent on thevalence of M" and the other symbols used are the same as identifiedabove. For example, instead of potasslum ferricyanide, K Fe(CN) thereare used and so forth. Examples of the preparation of such startmgmaterials are:

and

(II) K Fe CN) Cl+ H O K 1 6 (CN) H O+KCl They, also, may be prepared byboiling a material such as K Fe(CN) in aqueous KCI, oxalic acid or othersalt and so forth. Still other methods can be used. For exam le, seeCyanogen Compounds, Williams, 2nd ed., 1948, Edward Arnold and 00.,London, p. 252 and elsewhere.

The salts should be reacted in substantial concentration in aqueousmedia at room tempreature and, also, preferably in air or underatmospheric pressure. However, heat can be used and the catalyst can beprepared under conditions substantially or entirely free of oxygen. Thesalts which are used are the chloride, fluoride, bromide, iodide,oxynitrate, nitrate, sulfate or carboxylic acid salt, such as theacetate, formate, propionate, glycolate and the like salt of a M elementof the group as defined above or other M salts and mixtures thereof.Preferred are the M halide salts or halide salt forming materials sincethey provide catalysts having the best activity. An excess of the M saltis usually :reacted with a Na, K, Li, Ca etc. M cyanide compound and soforth. Mixtures of these salts can be used.

If the resulting precipitate is then just filtered or otherwiseseparated from the water, preferably by using a centrifuge and driedwithout further washing, it has been found that the precipitated complexis non-catalytic, that is, it fails to polymerize the organic oxides inany practical amount.

Apparently extraneous ions in the solution used to form the precipitateare easily occluded with the complex. Anions (Cletc.) coordinate to thepositively charged metallic ions in the lattice, and cations (Kcoordinate to the negatively charged nitrogen atoms of the cyanidebridging groups. These ions, especially those anions coordinating to orassociated with the M atom, inhibit catalytic activity or prevent thecomplex from causing appreciable polymerization. Additionally, theseions, for example easily ionizable Cl may, terminate the polymer chain.

On the other hand, if the complex is treated or washed one or more timeswith water, some or a substantial number of these occluded ions areremoved from the precipitate or from the surface of the crystal latticeand the complex becomes an active catalyst for the polymerization oforganic cyclic oxides. It is desired to remove all or a substantialamount of these occluded ions to enhance as much as possible thecatalytic activity of the complex. However, from a practical standpointit may not be possible to remove all of them due to the steps and timesrequired. Moreover, some of these ions are probably trapped in thecrystal lattice and cannot be removed easily. However, their presenceshould be reduced as much as possible. After the water wash the complexwill have an appreciable amount of water depending on the number ofwashings and the degree of drying following water washing. Theseresulting catalysts will then have the following rational formulae:

where d is a number and where M, M, CN, X, a, b, c, r and t have thesignificance as defined supra. If the catalyst is dried or gently heatedfor extended periods of time d can be or approach zero.

Moreover, to obtain the best activity of the catalysts forpolymerization, an organic material is added to the catalyst precipitatepreferably before it is centrifuged or filtered, is mixed with the waterduring washing of the precipitate, is used alone as the washing mediumprovided it replaces or dissolves the occluded ions, or is used to treator wash the precipitate after it has been washed with water to replaceat least a portion of the water. Sufficient of such organic material isused to effect these results in order to activate and/or enhance theactivity of the catalyst. Such organic material, also, should desirablycoordinate with the M element or ion and should desirably be one or morerelatively low molecular weight organic materials. The organic materialshould preferably be water miscible or soluble or substantially so, havea substantially straight chain or be free of bulky groups and have up to18 carbon atoms, even more preferably only up to 10 carbon atoms, and bea liquid at room temperature.

Examples of organic materials for use in treating the double metalcyanide catalyst to afford polymers of inherent viscosities inisopropanol of up to about 2.5 are alcohols, aldehydes and vketones suchas methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol,and t-butyl alcohol; formaldehyde, acetaldehyde, propionaldehyde,butyraldehyde, i-butyraldehyde, glyoxal, benzaldehyde and tolualdehyde:and acetone, methyl ethyl ketone, 3-pentanone, 2-pentanone, andZ-hexanone. Ethers such as organic cyclic polyethers are also usefulaffording generally polymers of intrinsic viscosities up to about 3.6.Examples of such cyclic ethers are rn-dioxane, p-dioxane,trioxymethylene, paraldehyde and so forth. Aliphatic saturatedmonoethers are also useful. Acyclic aliphatic polyethers are preferredsince catalysts treated with them afford polymers having intrinsicviscosities of from about 4 to about 7. Examples of such ethers, such asaliphatic ethers, are ethyl ether, l-ethoxy pentane, bis-(b-chloroethyl)ether, bis-(b-ethoxy ethyl) ether or diglyet, butyl ether, ethyl propylether, bis-(b-methoxy ethyl) ether or diglyme, ethylene glycol dimethylether, triethylene glycol dimethyl ether, dimethoxy methane, acetal,methyl propylether, diethoxymethane, octaethylene glycol dimethyl etherand so forth of which the acyclic polyethers are preferred. Still otherorganic complexing agents can be used such as the amides, esters,nitriles and sulfides of which the following are examples: formamide,acetamide, propionamide, butyramide, and valeramide; amyl formate, ethylformate, n-hexyl formate, n-propyl formate, ethyl ethanoate, methylacetate, ethyl acetate, methyl propionate, and triethylene glycoldiacetate; acetonitrile, propionitrile and butyronitrile; and dimethylsulfide, diethyl sulfide, dibutyl sulfide, dipropyl sulfide, and diamylsulfide and so forth. Preferred are ethers having more than one oxygenatom and which form a chelate bond with respect to M. Mixtures of theseorganic treating agents can be used. Excess of these organic treatingagents which are not complexed with the catalyst, especially the highboiling compounds, can be removed by extraction with pentane, hexane andso forth.

After treatment with the above organic material the catalysts have thefollowing rational formulae:

In these formulae d can be a number, fractional number, or zero and e isa number which, since the catalyst is a nonstoichiometric complex inwhich various amounts of H 0 and R may :be bonded to the various Ms, maybe a fractional number rather than an integer. e is zero when thecomplex is not treated with R. R is one or more of the complexingorganic amides, alcohols, aldehydes, esters, ethers and so forth shownabove. M, M, CN, X, a, b, c, r and t have the significance as discussedabove. In general, d and e will have values corresponding at least inpart to the coordination number of M. However, both the H 0 and R andcan be occluded in the crystal lattice. In general the sum of theoxygen, nitrogen and/ or sulfur or other coordinating atoms at H 0 and R(depending on the organic complexing agent) is equal to from about 0.1up to about 5.0 g-atoms maximum per g-atom of M. Subsequent drying orheating of the catalyst to remove all of the H 0 and/or R results in aloss or a substantial decrease in the catalytic activity of thecatalyst.

As shown by the previous formulae if the organic complexing material isnot used, R will not be present, and hence, e can be zero. Thus, thegeneral formula for these catalysts is M,. (K),,-(H O),, -(R) where M, HO, R, a, c, d, and e have the significance as indicated above, where dand 2 also can be or approach zero, where D is selected from the groupconsisting of M'(CN), and

and where M, CN, X, b, r and t have the significance as indicated above.With regard to the subscripts in the above formulae, number includeswhole numbers as well as fractional numbers.

It is to be noted that if the catalyst is merely filtered or centrifugedfrom the solution in which it was prepared and washed with one of thepolymerizable cyclic oxide monomers, it shows little or no catalyticactivity for subsequent polymerization of said monomers. On the otherhand, if the catalyst is washed with water and the ether, or the etheror other organic complexing compound as described above, andsubsequently with one of the polymerizable cyclic oxide monomers astorable initiator for polymerization is obtained.

After the washing steps the precipitate or catalyst can be used as such.However, it is preferred to dry it to remove excess treating agent andany remaining easily removable H O and to provide it in a form which iseasily handled. Such drying is readily accomplished by subjecting thecatalyst to a vacuum or by heating it in air or in an inert atmosphereat a temperature up to about 100 C. It is much preferred to dry under avacuum (for example 0.51 mm. Hg) at low temperature, for example aboutroom temperature (25 C.) or in a stream of air, nitrogen or inert gas at25 C. or at least at a tempera ture above about 5 C. The heat-treatedcatalyst has generally to be used at higher concentrations than thevacuum-treated catalyst. As the temperature during drying is increased,the activity of the catalyst for polymerization is decreased. Thus, hightemperatures are to be avoided. 200 C. may be considered as a maximumtemperature. During heat treatment it is believed that some of theoxygenated and other organic treating compounds weakly coordinated to Mmay be lost to leave voids in the crystal lattice, and the atoms in thecrystal lattice may rearrange to satisfy the cordination requirements ofthe metals. Heating may also remove CN- as (CN) and M. Also, themolecular weight of the catalyst can increase, and the number of exposedmetal ions on the surface of the catalyst or the active sites can bereduced, thus reducing the activity of the catalyst for epoxide andoxetane polymerization. It, thus, is preferred that the drying stepleave as many as possible M ions exposed in the lattice of the complexand that the catalyst be in finely divided or particulate form to obtainthe best results for polymerization. Moreover, freshly prepared(precipitated, washed and dried) catalysts are preferred rather thancatalysts which have been aged or stored for extended periods of timesince the catalysts decompose slowly when stored. The catalyst can bestored for longer times at lower temperatures.

The organic cyclic oxides to be polymerized include any ayclic oxidehaving an oxygen-carbon ring in which an oxygen atom is joined to 2 or 3carbon atoms in the ring which will open and polymerize with the same orother cyclic oxide monomers and having up to a total of 70 carbon atomsor more. These monomers, also, may contain 1, 2 or more, preferably only1, aliphatic carbonto-carbon double bonds. The alkenyl, nitro, ether,ester and halogen (except easily ionizable halogen substitutedderivatives) substituted derivatives of these cyclic oxides can likewisebe employed. The use of monomer mixtures having cyclic oxide monomer(s)containing aliphatic carbon-to-carbon double bond unsaturation in minoramounts, the balance being the saturated cyclic oxide monomer(s),permits the resulting copolymer to be cured readily with materials suchas sulfur and the like. A very useful mixture is one containingpropylene and/or 1,2- butylene oxide or other saturated oxide in anamount of from about to 99.5 mol percent and allyl glycidyl ether, vinylcyclohexene monoxide and/or butadiene monoxide or other unsaturatedoxide in an amount of from 20 to 0.5 mol percent to obtain acrosslinkable (by sulfur) copolymer. Minor amounts, about 05-20 molpercent, of a third, fourth or fifth etc. monomer, replacing part of thepropylene oxide and/ or allyl glycidyl ether etc. such as 1,2-buteneoxide, 2,3-hexene oxide etc. of from 4 to 12 carbon atoms, can be usedin making the copolymer to break the lengths of isotactic units in thecopolymer which are too short to be measured by X-ray. This may bedesirable, where only small amounts of an unsaturated monomer are used,to obtain more flexibility in processing and molding. These cyclicoxides should be pure or essentially pure to obtain the best results orthey should be free or essentially free of materials like H O which mayinhibit polymerization.

Examples of useful cyclic oxides are ethylene oxide (1,2-epoxy ethane),propylene oxide, 1,2-butene oxide (or 1,2-epoxy butene), 2,3-buteneoxide, 1,2-dodecane monoxide, isobutylene monoxide, styrene oxide, 1,2-pentene oxide, isopentene oxide, 1,2-diisobutylene oxide, 1,2-hexeneoxide, 2,3-hexene oxide, 1,2-heptene oxide, allyl glycidyl ether,isoheptene oxide, octene oxide, nonene oxide, decene oxide, hendeceneoxide, methyl glycidyl ether, ethyl glycidyl ether, vinyl cyclohexenemonoxide, nitro ethylene oxide, phenyl glycidyl ether, 3-methyl-3,4-epoxy butene-l, butadiene monoxide, glycidyl methacrylate,2,3-diisobutylene oxide, dicyclopentadiene monoxide, isoprene monoxide,oxetane (C H O), tolyl glycidyl ether, 3,3-dimethyl oxetane, 3-n-nonyloxetane, 3-allyl-3- methyl oxetane, 3-vinyl-3-methyl oxetane,pentadecene oxide, 3,3-diethyl oxetane, 3-ethyl-3-butyl oxetane, 3-chloro-methylene oxetane, 3-chloro methyl-3-methyl oxetane,3-methyl-3-ethyl oxetane, 1,2-epoxy pentacosane, 1,4-dichloro-2,3-epoxybutane, allyl epoxy stearate, 1,2- hexaeontene oxide, 1,2-heptaconteneoxide and other cyclic oxides. These cyclic oxides should preferablyhave a total of from 2 to 25 carbon atoms. Of these materials it is evenmore preferred to use the lower molecular weight cyclic oxides such asethylene oxide, propylene oxide, butylene oxide, etc. containing from 2to 12 carbon atoms with minor amounts of unsaturated cyclic oxides, suchas allyl glycidyl ether, butadiene monoxide and vinyl cyclohexenemonoxide, etc. containing up to 12 carbon atoms. Mixtures of 2, 3, 4, 5or more of these cyclic oxides can be used for polymerization.

One or more of the above cyclic oxides can be reacted with one or morecyclic oxides having 2, 3 or more rings of from 2 to 3 carbon atoms and1 oxygen atom, preferably in a minor molar amount. Examples of thesecyclic oxides (ie, di, tri, etc. epoxides and/or oxetanes) are:butadiene dioxide, vinyl cyclohexene dioxide, limonene dioxide, thediglycidyl ether of bisphenol A, the diglycidyl ether of pentanediol,the reaction product of the diglycidyl ether of pentanediol andbisphenol A, the reaction product of the diglycidyl ether of pentanedioland a polyalkylene and/or arylene ether glycol, (3,4-epoxy-6- methylcyclohexyl methyl)-3,4-epoxy-6-methyl cyclohexane carboxylate,1-epoxyethyl-3,4-epoxy cyclohexane, diglycidyl ether, bis(3-oxetane)butane, bis(3-oxetane) hexane, dipentane dioxide the reactionproduct of epichlorohydrin and trihydroxyl diphenyl dimethyl methane,the reaction product of epichlorohydrin and phloroglucinol, the reactionproduct of epichlorhydrin and erythritol, the reaction product of3-chloro oxetane and his phenol A, the reaction product of 3-chlorooxetane and trihydroxyl diphenyl dimethyl methane, the reaction productof 3-chloro oxetane and hexanetriol-l, 2, 6 or pentaerythritol, and thelike and mixtures thereof.

Alkylene oxides or epoxides are well known. They can be prepared by thereaction of alkenes such as propylene, ethylene, Z-butene,butadiene-1,3, divinyl benzene etc. with perbenzoic acid, peracetic acidand so forth in an inert solvent at low temperatures followed bydistillation or other separation. Other methods can be used such asshown in the Journal of the American Chemical Society, 78, 4787 (1956).Also Oxetanes also are well known. They can be made by the preparationof a NaOH solution of a 1,3-glycol which is then dripped into sulfuricacid to close the ring and split out water. An alternative method is asfollows:

HCl CHsCOOH HO CH2CH2CH2OH HOCH2CH2CH2Cl H2CCH2 KOH CIH2CCH2CH2OCOCH3trimethyleneoxide, H2

Another method is to heat a dialdehyde'in the presence of acetaldehydeand aluminum isopropoxide; distill off the acetone to get the aluminumsalt; hydrolyze to remove the aluminum to obtain and then add thiscompound to a NaOH solution and drip the solution into sulfuric acid toobtain ring closure and the splitting out of H 0.

The catalyst is used in a minor amountby weight only suflicient tocatalyze the reaction. Large amounts are usually wasteful and may intime cause reversion or subsequent decomposition of the polymer. Ingeneral, there is used a total of from about 0.001 to 10.% by weight ofthe catalyst based on the total weight of the polymerizable cyclic oxidemonomer or monomers employed during polymerization. However, it ispreferred to use from about 0.01 to 0.50% by weight of the catalystsbased on the total weight of the monomer(s).

The monomers may be polymerized with the catalyst in mass, or in solvent(which can facilitate handling and transfer of heat). They, also, shouldbe polymerized under inert and/or non-oxidizing conditions, for example,under an atmosphere of nitrogen, argon, neon, helium, krypton or otherinert atmosphere. Alternatively, the inert gas can be omitted and themonomer polymerized only under pressure from any vaporized solvent ifused or vaporized monomer. In some instances the polymerization can beconducted in polymerizers open to the air provided the air is free ofmaterials which would inhibit polymerization (i.e., conversion ormolecular weight) and especially free of H 0, although this procedurecan be hazardous for some of the monomers are flammable. The monomershould be soluble in the solvent which should be an inert ornon-reactive solvent. Examples of useful solvents are heptane, octane,cyclohexane, toluene, benzene, trimethylpentane, n-hexyl chloride,n-octyl chloride, carbon tetrachloride, chloroform, trichloroethyleneetc. Since many of the reactants are volatile the polymerization shouldbe conducted in a closed container and may be under pressure. Thereactor is preferably operated at a total pressure of 1 atmosphere orsomewhat less. Polymerization can be conducted at temperatures of fromabout 0 C. to 100 C. although somewhat wider temperature ranges can beused. Preferably temperatures of from about 15 C. to 35 C. are used forpolymerization. An induction period of aboutMz-Z hours or more may beobserved with some of the catalysts. If the polymer dissolves in thesolvent, it can be precipitated with a nonsolvent and recovered, or thesolvent can be separated from the polymer by distillation orevaporation. The catalyst or catalyst residues can be removed if desiredby dissolving the polymer in a solvent, adding dilute aqueous KOH andthen reprecipitating or by treating a 10 solution of the polymer with HO or NH OH and centrifuging. The necessity of removal of the catalystwill depend upon the ultimate use of the polymer. It is very desirableto polymerize while agitating the monomer(s), catalyst and solvent, ifused.

Since the reaction is exothermic and since some monomers may polymerizevery rapidly in the presence of the catalyst, it may be desirable toreduce the concentration of the catalyst or to use a solvent as above asdiluent.

Gel formation during polymerization with unsaturated monomers is notusually observed using the double metal cyanide catalysts, andconsequently gel inhibitors are not normally required. Antioxidants orantidegradants such as phenyl beta naphthylamine, PBNA, or otherantidegradants are desirably added prior to or after polymerization toavoid degradation which might occur in the presence of these catalystswhich may catalyze oxidation. PBNA my be used in an amount by weightapproximately equal to the amount of the catalyst during polymerization.Some antidegradan-ts may retard polymerization and should be added afterpolymerization.

The polymers and copolymers etc. obtained by the method of the presentinvention have an average molecular weight of at least 20,000. Most ofthem have a high average molecular weight of from about 500,000 to1,000,000 or higher, as shown by their high viscosities. As anindication of the amorphous nature of most of these polymers a rubberycopolymer of about 97 mol percent propylene oxide and 3 mol percentallyl glycidyl ether is relatively soft and gives low tensile values(about 350 p.s.i.) when cured as a gum stock. When loaded with 40 p.p.h.of HAF black, tensile strengths of up to 2300 p.s.i. are observed. X-raydiffraction of the black loaded cured stock when stretched showed a lowdegree of crystallinity.

The resinous and rubbery polymers of this invention are useful ascoatings or impregnants for fabrics, films for packaging materials,belts, elastic fibers, adhesives, hose or tubing, and in making tires,shoe heels, raincoats, rubbery laminates, upholstery materials, floormats and tiles, carpet and rug backings, gaskets, molded articles, golfball covers, centers and cores, sponges or other cellular products,encapsulating compounds and the like. Low molecular weight solid orgrease-like polymers of this invention are useful as plasticizers andextenders for natural and synthetic resins and rubbers as well as forthe high molecular weight polymers of the present invention.

The polymers may be compounded or mixed with the usual rubber andresinous compounding materials such as curing agents, anti-degradants,fillers, extenders, ultraviolet light absorbers, fire resistantmaterials, dyes, pigments, plasticizers, lubricants, other rubbers andresins and the like. Examples of useful materials which can becompounded with these rubbers, resins and polymers are zinc oxide,stearic acid, zinc stearate, sulfur, organic peroxides,Z-mercaptobenzothiazole, bis-(morpholyl) disulfide, bis(benzothiazyl)disulfide, zinc dimethyl dithiocarbamate, tetramethyl thiuram disulfide,carbon black, TiO iron oxide, calcium oxide, SiO and SiOg containingmaterials, aluminum oxide, phthalocyanine blue or green, asbestos, mica,wood flour, nylon or cellulose fibers or flock, clay, barytes, dioctylphthalate, tricresyl phosphate, non-migrating polyester plasticizers,phenyl beta naphthylamine, pine oil, mineral oil, hydroquinonemonobenzyl ether, mixtures of octylated diphenyl-amines, styrenatedphenols, aldol alpha naphthylamine, diphenyl amine acetone reactionproducts, antimony oxide, asphalt, coumarone indene resin, naturalrubber, polyisoprene, butadiene-styrene rubber or resin,polyethylene-propylene rubbers, a 60/30/10 ethylene-propylene-butadieneterpolyrner, nitrile rubber, polybutadiene, acrylonitrilestyrene resin,polyesters, polyethers, polyester and/or ether urethanes, polyvinylchloride and the like and mixtures thereof. Polymers of the presentinvention may be cured by sulfur and the like or sulfur furnishingmaterials, organic peroxides, other curing and crosslinking materials,irradiation and so forth.

It is not precisely known what occurs to make the double metal cyanidecomplexes, especially those treated with the above organic complexingmaterials (ether, etc.), so useful in polymerizing organic cyclicoxides. While the following discussion relates to treatment of thedouble metal cyanide catalyst with ethers, it will be appreciated thatit will generally also apply to treatment of such catalyst with theother organic treating agents shown above. It has been shown that, forexample, with respect to zinc hexacyanoferrate, as an illustration, whenthe precipitate is washed with dioxane, a more effective catalyst isproduced. During this treatment with dioxane it is believed that anumber of reactions takes place: (1) some of the chloride ions in thelattice are oxidized, resulting in the reduction of Fe ('III) to Fe(II); (2) the chlorine from reaction (1) reacts with the water and etherpresent during the wash-treatment to give Cl'", and chlorinated ether;(3) the successive washes remove some of the products of reaction (2);and (4), the oxygen atoms of the ether apparently coordinate to the zincions in the lattice, rearranging the lattice structure by insertingdioxane groups between the zinc ions as follows:

Thus, in the case of some of the dioxane-zinc hexacyanoferratecomplexes, elemental analyses revealed that they were apparentnonstoichiometric complexes having the formula Z113 (CN)6] 2( 4 a 2)x( 2y where y=1 to 2 and x=2.5 to 3.1. According to infrared and elementalanalyses some of the dioxane in the complex may be chlorinated and someof the H may be in the form of OI-I, or 0- groups. As ordinarilyprepared, these complexes generally contained from about 4 to 5% Cl anda smaller amount of K+.

If the catalyst is prepared with 'Zn(NO instead of ZnCl approximately50% of the normal amount of dioxane is incorporated in the catalyst.This catalyst is not as effective as the one prepared from the chlorideas shown by Example 2 below.

Although a great part of the iron in the ether (or other organic complxing moiety)-zinc hexacyanoferrate complex is believed to be Fe II), asa result of the oxidation-reduction reaction that occurs duringpreparation, the dioxane complex prepared from ZnCl and K4Fe(ON) is notas active even at polymerization temperatures of 80 C. Analyses showedthat a reduced amount of dioxane was incorporated in such complexes andthe chlorine content was high.

The reduced catalytic effects when using Zn(NO or K Fe(CN) in thepreparation of the catalyst complex is apparrently related to themechanism of the etherhexacyanoferrate reaction. This mechanism may beviewed as follows. As the chloride ions of the surface zinc ions in thecrystal lattice transfer electrons into the Zn NC-Fe grouping, ethermolecules can displace the resulting chlorine atoms and form ether-zinccoordinate lbonds. For example,

(Note: y in the above equation may not be same as in the precedingformulae.)

The driving force for this reaction is the removal of C1 by solution ofthe gas in the water and ether and the reaction of C1 with the ether.

This oxidation-reduction reaction and displacement of the chlorine byether is accompanied by a change in the crystal lattice. According toelemental and infrared analyses, most of the zinc ions in the latticeappear to form coordination bonds with from 1 to 4 oxygen atoms. Theoxygen atoms of both the water and the ether are involved in thiscoordination. X-ray analysis and density measurements appeared toconfirm this lattice change. Thus, the oxygen atoms of the ether competewith the CN groups of the Fe (ON) anion to produce a polymeric structurewith more exposed zinc ions as shown below:

N o I This process of opening up the lattice is aided by the presence ofwater during the ether treatment. Apparently, the water dissolves Fe(CN)anion sections in the lattice that are coordinated to K+ ions, and moreof the lattice becomes exposed to the ether during thehexacyanoferrateether reaction.

Moreover, it appears from experiments that water acts as achain-transfer agent in organic oxide polymerization with thesecatalysts. Therefore, the best catalyst for producing a polymer of highmolecular weight is preferably one containing the least amount of water.One technique for removing water from the lattice structure is todisplace the water with ether and remove the former by azeotropicdistillation as shown by Example 2B below. The distillation is bestcarried out under vacuum at room temperature or t-hereabouts, i.e. 5 to40 C., in order to prevent decomposition of the complex which may occurat elevated temperatures as discussed supra. In any event temperaturesshould not go above or 200 C. as discussed supra or below about 5 C.Hexane or other relatively low 'boiling, inert, and essentiallywater-insoluble solvents such as heptane, toluene, benzene, pentane,2-chlorobutane, cyclohexane, cyclopentane, ethylene chloride, and butanecan be used in this distillation to separate the water from the ether asthe distillate collects in a trap. In this way, all displaceable wateris removed, however some water invariably remains trapped in thelattice. Other methods can be used to remove the water.

Also experiments indicate that chloride ions can inhibit thepolymerization reaction (compare Examples 2B and C, and 6A and B below.Several methods for reducing the ionizable chlorine or other ionizableanions in the catalysts can be used. For example, in one method thecatalyst is washed with a solution containing ether and water and thesoluble chloride salt is removed. In another method the zinchexacyanoferrate is prepared by reacting compounds such as Ca [Fe(CN)AlFe(CN) or Li Fe(C-N) with ZnCl The corresponding halide that forms andoccludes on the crystals of Zn [Fe(CN) is then removed by the etherduring the washing operation. When the preparations are made with K Fe(CN) etherinsoluble KCl is produced. However, when zinc hexacyanoferrateis prepared by the second method above, ether (organic treating agent)soluble CaCI A1Cl3, or LiCl is produced. Also, where ions such as Cl arecovalently bound to the complex, they do not apparently adversely affectpolymerization of the cpoxides and oxetanes. In fact, the organiccomplexing materials like the chlorinated ethers can improve theefiiciency of the catalyst, because the halogenated ethers can bedisplaced more readily by the epoxides and oxetanes to startpolymerization than the nonhalogenated ethers.

When the catalyst is treated with polyethylene glycol ethers, a veryactive catalyst is obtained. The y apparently form a chelate bond to thezinc ion. The formation of a chelate complex increases the driving forceof the hexacyanoferrate-ether reaction and makes for a very open The useof diglyme and diglyet (dimethyl and diethyl ethers, respectively, ofdiethylene glycol) in the usual catalyst preparation was found toincrease the efliciency of the catalyst from 500 g. polymer/ g. catalystto 850 g. polymer/ g. catalyst.

Moreover, the addition of a substantial amount, such as 3070% by volumeof the total fluid, of the ether (or other organic treating agent) tofreshly precipitated hexacyanoferrate in water greatly enhanced theactivity of the catalyst, more than doubled amount of polymer per unitweight of the catalyst, (see Example 6C below): the efficiency increasesto 2000 g. polymer/ g. catalyst. This catalyst also produces a polymerof vary high molecular weight. According to elemental analysis, thiscomplex may have some (ZnCl) ions in its structure.

It, thus, would appear that the best catalysts for oxide polymerizationare those that contain the greatest amount of Zn-O ether bonds, ratherthan Zn-O H bonds, and the least amount of ionizable chlorine. The moreactive catalysts, also, are prepared by using an excess of zincchloride, and adding the K Fe(CN) solution to the chloride. Accordingly,it is seen that the present invention provides a novel way forpolymerizing cyclic oxides and methods for enhancing the activity of thecatalysts to obtain higher molecular weights, greater catalystefficiency and so forth.

The following examples will serve to illustrate the present inventionwith more particularity to those skilled in the art:

Example 1 Relatively pure zinc hexacyanoferrate (III) as catalyst Temp.C. 15 80 Time, hrs. 24 Percent wt. Catalyst 1 0.2 Percent wt. PBNA 2 0.2

M01. percent AGE 3 Feed 3.0

Polymer 1.9 Percent conversion 40 Vis. 1.6

Based on weight of monomer(s) charged to the polymerization bottle.

Based on the weight of the monomer-(s) charged to the polymerizationbottle.

3 M01 percent of allyl glycidyl ether charged to lthe polymerizatienbottle and In the resulting polymer, balance being propylene oxide.

1 4 Intrinsic viscosity in isopropanol at 60' C.

If zinc hexacyanoferrate was prepared by combining 15- 20% (wt.) aqueoussolutions of zinc chloride and potassium hexacyanoferrate (III), theresulting precipitate, after drying under vacuum over P 0 was relativelyinactive as a catalyst for epoxide polymerization due to excessiveamount of ionizable chlorine being present and in contrast, if the zinchexacyanoferrate was thoroughly washed with hot water as shown above,the dried precipitate did copolymerize propylene oxide and allylglycidyl ether at 80 C. However, the molecular weight of the polymer wasrelatively low, and the efficiency of the catalyst was pooronly 200 g.polymer/ g. catalyst.

In Example 1 above, the dried catalst, generally an equal weight of PBNA(phenyl B-naphthylamine), and a magnetic stirring bar were charged intoa dry, crowncapped beverage bottle. The bottle was capped and evacuatedat 1 mm. Hg for one hour to remove any occluded moisture and, finally,the monomers were charged into the evacuated bottle. Polymerization wascarried out in a constant temperature bath. The monomer-catalyst slurrywas agitated by a magnetic stirrer, and agitation was stopped when thepolymers began to soilidify. The P0 and AGE were purified before beingcharged to the evacuated polymerization bottle by careful fractionation.Analysis by Karl Fischer reagent showed that the monomers contained lessthan 1'0 p.p.m. water. Pressure in the bottles at the beginning ofpolymerization was about 1 atmosphere or slightly less.

Example 2 similar to the foregoing as follows:

Catalyst Conc. Pzn. Reaction Percent Inherent wt. percent on Temp.,Time, Conversion Viscosity 1 Monomer 0 Hrs.

Measured in benzene at approximately 0.05 g. polymer/ 100 cc. benzene.

When the same procedure was followed except that methyl ethyl ketone wasused in place of the acetone and except that the MEK was not added tothe water-precipitate slurry the following results were obtained:

Measured in benzene at approximately 0.10 g. polymer cc. benzene.

- Not determined.

In an alternative procedure the zinc ferricyanide precipitate in H O wasmixed with alcohol, filtered, washed with acetone, vacuum dried at roomtemperature to re move occluded acetone, H O etc. and heated in a streamof N (lamp grade) at about 100 C. to remove more H O, acetone etc.although temperatures up to about 200 C. for 5 hours have beenused. Onegram of this treated catalyst provided g. of a copolymer of PO and AGEhaving an inherent viscosity in benzene of 3.84 after 24 hours at 30 C.When the step of heating the catalyst in a stream of hot N was omitted,the catalyst was so active that the polymerization bottles ruptured.

Example 3 ZnCl was reacted in aqueous media with Na Fe (CN) N to providea catalyst having the general base formula ZnFe(CN) NO. The catalyst wasseparated from the water, washed with acetone and vacuum dried at roomtemperature. This treated catalyst was then used to polymerize propyleneoxide by methods similar to the above procedures as follows:

Catalyst, Wt. React. Time, Percent Inherent Percent on Temp., Hrs.Conversion Viscosity 1 Monomer C.

1 Measured in benzene at approximately 0.10 g. polymer/100 cc. benzene.

Example 5 A catalyst having the general base formula was prepared bymethods similar to the above. After separation of the catalyst from thewater, one portion was washed with acetone and the other portion waswashed with dioxane. The thus treated catalysts were then used for thepolymerization of propylene oxide generally according to the precedingmethods as follows:

Catalyst Wt. Percent Temp., Time, Percent Remarks Treat. Cat. on 0. Hrs.Conver- Agent Monomer sion Acetone. 0. 5 80 48 34 Light grease. Dioxane0. 5 80 48 18 D0.

Example 6 Several catalysts were prepared by reacting an excess of ZnClseparately with Ca [Co(CN) K C0(CN) Na CO(CN) and Li Co(CN) Theprecipitated catalysts were washed with acetone and vacuum dried at roomtemperature. They were then used to polymerize propylene oxide generallyaccording to the methods described supra as follows:

Salt Used Wt. Percent React. React. Percent Inherent to React Cat. onTime, Tcmp., Conver- Viscosity With ZnClz Monomer Hrs. C. sionCa3[C0(CN)e]z 0. 08 96 25 100 1 1. 82 K Co(CN)-, 0.2 24 25 82 1 3. 25NaaCo(CN)s 0. 5 25 25 92 3 1 Li3Co(CN)t. 0. 5 72 25 80 3 1 1 Inisopropanol.

1 In benzene at approximately 0.10 g. polymer/100 cc. benzene.

Estimated.

Norm-This example shows that other ON salts can be reacted with ZnClz tomake catalysts.

Example 7 K Fe(CN) was reacted in aqueous media with various zinc saltsto make precipitates which were filtered from 16 the media, washed withacetone and vacuum dried at room temperature. The resulting catalystswere then used to polymerize propylene oxide by methods similar to theforegoing as follows:

Zn Salt Used to Prepare Pzn. Temp., Wt. Percent Yield,

Catalyst 0. Catalyst on Percent Monomer ZnCla 25 0. 1 41 ZnBrz 25 0. 240 0. 2 57 ZI1(NO3)z 80 0.5 20

These results show that other zinc salts can be used in the preparationof useful catalysts.

Example 8 Zinc hexacyano cobaltate (III) was prepared in aqueous asfollows:

The precipitate obtained was for three times washed with acetone andcentrifuged. 'It was finally vacuum dried at room'temperature. It waspulverized and gave a white powder. 0.1 g. of this acetone washedpowdered Zn [Co(CN) catalyst was placed in a polymerization bottle, andthen 10 g. of oxetane was added. Polymerization was conducted in thecapped polymerization bottle under nitrogen without solvent for 41 hoursat 80" C. to give a yield of polymer of 87%. This oxetane polymer had aviscosity in isopropanol of 0.72 and an ash of 0.83%. The polymer was arubbery clear gum and was somewhat snappy.

Example 9 A Zn [Co(CN) catalyst using acetone as the complexing agentwas prepared in a manner similar to that of the preceding example. 0.04wt. percent of this catalyst on the weight of the monomer, 1,2-buteneoxide, under nitrogen in a capped polymerization bottle at 25 C. for 24hours gave a yield of 60% of a tacky solid of homopoly 1,2-butene oxide.

It is to be understood that in accordance with the patent laws andstatutes, the particular compositions, products and methods disclosedherein are presented for purposes of explanation and that variousmodifications can be made in these compositions, products and methodswithout departing from the spirit of the present invention.

What is claimed is:

1. A composition comprising a double metal cyanide complex compound freeof hydrogen as a cation, wherein one of the metals of said complexcompound is selected from the group consisting of Zn (II), Fe (11), Fe(III), Co (111), Ni (II), Mo (IV), Mo (VI), Al (III), V (IV), V (V), Sr(II), W (IV), W (VI), Mn (II), and Cr (III), and mixtures thereof, andwherein the other metal of said complex compound is selected from thegroup consisting of Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr(III), Mn (II), Mn (III), V (IV), and V (V), and mixtures thereof,containing, in an amount sufiicient to increase the activity of saidcomplex for the polymerization of organic cyclic oxides, at least oneorganic material selected from the group consisting of an alcohol havingonly hydroxyl functionality, an aldehyde ha ing only aldehydefunctionality, and a ketone having only ketone functionality, saidorganic material consisting of carbon, hydrogen and oxygen, having up to18 carbon atoms, being inert to polymerization by said compound andfurther being complexcd with said compound, said compound containing atleast a majority of CN- bridging groups.

2. A composition useful in polymerizing organic cyclic oxides and havingthe general formula:

where D is selected from the group consisting of M'(CN) andM'[(CN),(X),]

17 where M is at least one metal selected from the group consisting ofZn (II), Fe (II), Fe (III), Co (11), Ni (11), Mo (1V), Mo (VI), AlII-I), V (IV), V (V), Sr (II), W (IV), W (V I), Mn (II), and Cr (III),where M is at least one metal selected from the group consisting of Fe(II), Fe (-111), Co ('11), Co (111), Cr (II), Cr (III), Mn (II), Mn(III), V (IV), and V(V), where X is at least one material selected fromthe group consisting of F-, Cl, Br, I-, OH NO, 00, B 0, N0 C 031 SO CNO,CNS-, NCO, and NCS, where R is at least one organic material consistingof carbon, hydrogen and oxygen, having up to 18 carbon atoms, beingsubstantially water miscible and being selected from the groupconsisting of an alcohol having only hydroxyl functionality, an aldehydehaving only aldehyde functionality, and a ketone having only ketonefunctionality, said organic material being inert to polymerization by,and being complexed with, M,. (D) (H O) of said formula, where a, b andc are numbers whose values are functions of the valences andcoordination numbers of M and M, the total net positive charge on Mtimes a being essentially equal to the total net negative charge on (D)times 0,

where r is greater than t, where r is a number, where t is a number,where d is zero or a number, and where e is a number sufficient toincrease the activity of M,(D) -(H O) for the polymerization of saidorganic cyclic oxides.

3. A composition according to claim 2 where M is Zn (II), M is Fe (II)and Fe III), t is zero, and the sum of the coordinating atoms of H 0 andR is equal to from about 0.1 to 5 g.-atoms per |g.-atom of M.

4. A composition according to claim 2 where R is a ketone.

S. A composition according to claim 4 where the ketone is acetone.

6. A composition according to claim 4 where the ketone is methyl ethylketone.

7. A composition according to claim 2 in which M is at least one metalselected from the group consisting of zinc (II), iron (II), cobalt (II)and nickel (II) and where M is at least one metal selected from thegroup consisting of iron (II), iron (III), cobalt (III) and chromium(III).

8. The method which comprises repeatedly washing a double metal cyanidecomplex compound, wherein one of the metals of said complex compound isselected from the group consisting of Zn (II), Fe (II), Fe (III), Co(II), Ni (II), Mo (IV), Mo (VI), Al (III), V (IV), V (V), Sr (II), W(IV), W (VI), Mn (II) and Cr. (III), and mixtures thereof and whereinthe other metal of said complex compound is selected from the groupconsisting of Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III),Mn (II), Mn (III), V (IV), and V (V), and mixtures thereof, said cyanidecomplex compound having a majority of CN- bridging groups, with anamount suflicient to increase the activity of said complex for thepolymerization of organic cyclic oxides of at least one organicmaterial, said organic material being selected from the group consistingof an alcohol having only hydroxyl functionality, an aldehyde havingonly aldehyde functionally, and a ketone having only ketonefunctionality, and said organic material consisting of carbon, hydrogenand oxygen, having up to 18 carbon atoms, being inert to polymeriztaionby said compound and further being complexed with said compound.

9. The method which comprises repeatedly washing a first-named compoundcomprising a precipitate having the general formula: M,,(D) (H O) withan amount sufiicient to increase the activity of said compound for thepolymerization of organic cyclic oxides of at least one organic materialconsisting of carbon, hydrogen and oxygen, having up to 18 carbon atoms,being substantially water miscible and being selected from the groupconsisting of an alcohol having only hydroxyl functionality, an aldehydehaving only aldehyde functionality, and a ketone having only ketonefunctionality, to provide a second-named compound having the generalformula: M,,(D),,-(H O) -(R) where in said formulae:

R is said organic material,

D is selected from the group consisting of M'(CN) n )r( )t]'b:

M is at least one metal selected from the group consisting of Zn (II),Fe (II), Fe (III), Co (II), Ni (II), Mo (IV), Mo (VI), Al (III), V (IV),V (V), Sr (II), W (IV), W (VI), Mn (II) and Cr (III),

M is at least one metal selected from the group consisting of Fe (II),Fe (III), Co (II), Co (III), Cr (II) Cr (III), Mn (II), Mn (III), V(IV), and V X is at least one material selected from the groupconsisting of F-, Cl, Br", I, OH, NO, 0 CO, H O, N0 1 C 081 CNO, CNS,NCO: and NCS,

a, b and c are numbers whose values are functions of the valences andcoordination numbers of M and M, the total net positive charge on Mtimes a being essentially equal to the total net negative charge on (D)times 0,

r is greater than t,

r is a number, 2 is a number,

d is zero or a number, and e is a number sufiicient to increase theactivity of said first-named compound for the polymerization of saidorganic cyclic oxides, said organic material being inert topolymerization by, and being complexed with, said first-named compound,and drying said second -named compound.

10. The method according to claim 9 where said second-named compound isdried at a temperature of from about 5 to C.

11. The method according to claim 9 where said drying is conducted in avacuum.

12. The method according to claim 9 wherein said second-named compoundis dried in a vacuum at a temperature of about 25 C.

13. The method according to claim 12 wherein said vacuum dried compoundis heated in a stream of gas at a temperature up to 200 C.

14. The method according to claim 9 where M is Zn (II), M is Fe (II) andFe (III), t is zero, and the sum of the coordinating atoms of H 0 and Ris equal to from about 0.1 to 5 g.-atoms per g.-atom of M.

15. The method according to claim 9 in which R is a ketone.

16. The method according to claim 15 where said ketone is acetone.

17. The method according to claim 15 where said ketone is methyl ethylketone.

18. The method according to claim 9 in which M is at least one metalselected from the group consisting of zinc (II), iron (II), cobalt (II)and nickel (II) and where M is at least one metal selected from thegroup consisting of iron (II), iron (III), cobalt (III) and chromium(III).

References Cited UNITED STATES PATENTS 2,152,716 4/1939 Van Wirt et al.106304 2,434,578 I/ 1948 Miller 44-67 3,065,250 11/1962 Levering 260429(Other references on following page) 3,427,334 19 20 OTHER REFERENCESTOBIAS E. LEVOW, Primary Examiner.

Williams Cyanogen Compounds, Edward Arnold and P- DEMERS, ssistant Exminer. C0,, London, 1948, pp. 178 and 213.

Cohn, Compt. rend. 223 (1946) pp. 10224. Pascal, Nouveau Traiti deChimie Minerale, v01. 18, 5 23-077; 252-428, 431; 260-2, 83, 88.3, 348,429.7, 1959, Masson et Cie, Paris, p. 192. 438.5, 439

